CN103172860B - A kind of preparation method of medlin particulate - Google Patents
A kind of preparation method of medlin particulate Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of medlin particulate. It is raw material that the present invention adopts diamines and dianhydride, prepares medlin particulate by ester-sour o. The features such as the prepared medlin particulate of the present invention has that degree of crystallinity is high, stable performance, specific area are large, compound with regular structure, and technique is simple, productive rate is high, reproducible, thereby be suitable for industrial production.
Description
Technical field
The present invention relates to material science, particularly a kind of preparation method of medlin particulate.
Technical background
Polyimides is one of macromolecular material that temperature classification is the highest in industrial practical application up to now, has simultaneouslyHigher mechanical strength, good dielectric properties, nontoxicity, chemical resistance corrosion and radiation resistance, extensively shouldFor fields such as Aeronautics and Astronautics, electric, mechanical, chemical industry, microelectronics. It uses form varied, comprises polyamides AsiaAmine film, polyimide insulative paint, polyimides photonasty coating, polyimides electrophoretic coating, polyimide binder,Polyimide powder, particulate, polyimides formed body etc.
Medlin particulate is due to existing polyimides, shows again that polymer particles specific area is large, adsorptivity is strongAnd the characteristic such as agglutination is large, have broad application prospects. For example, for catalyst carrier, there is wear-resisting, resistance to solventAnd the good characteristic such as high temperature resistant, and particle diameter is controlled; For separating of purifying, selectively good, resistance to solvent, dimensionally stable; Be used forPharmaceutical carrier, stability is high, good with cell membrane compatibility, can reach effect of slowly-releasing, target by certain blocking agent.Therefore, the exploitation of medlin particulate becomes important component part and the study hotspot of polyimides research gradually.
In recent years, the preparation of medlin particulate has in the literature institute and reports, the method for preparing medlin particulate has dispersionPolymerization, precipitation polymerization method, reprecipitation method and template etc. Publication number is CN1246489A's " polyamic acid and poly-Acid imide subparticle and their preparation method ", first the method is prepared the solution A that contains acid anhydrides and is contained diaminesSolution B, then two kinds of solution are mixed, reaction under continuous ultrasound stirs, separates out polyamic acid particulate, finally carries out sub-acylAmination obtains medlin particulate. But the method post processing difficulty, due under ultrasonication, causes the fragmentation of particulate, systemStandby medlin particulate surface topography heterogeneity, particle diameter distributes and cannot effectively control. Publication number is CN101230136A's" polyimide microparticle and preparation method thereof ", the method in the solvent that contains dispersant, add successively aromatic diamine andAromatic series dianhydride monomer, after stirring reaction a period of time, polyamic acid particulate is precipitated out from solvent, after separating, then willPolyamic acid microparticulate, in dimethylbenzene, adds hot reflux and carries out hot imidization, obtains medlin particulate. The method is madeStandby medlin particulate exists that sphericity is poor, pattern is different and bonds the deficiency such as serious. Publication number is CN101089030A" a kind of preparation method of polyimide microsphere ", the similar reppd method of the method, by the molten diamine monomer dispersant that containsSolvent in, then add dianhydride monomer to make polyamic acid solution in batches, through chemical imidization, obtain polyimide solution;Finally, dropwise add the aqueous solution that is dissolved with dispersant, make medlin particulate Precipitation from solution, centrifugation,Washing, oven dry obtain medlin particulate. This preparation method's process complexity, is difficult to control, and is difficult to ensure medlin particulateDispersiveness and homogeneity. Publication number be CN101703913A's " a kind of method of preparing polyimide microsphere ", the methodFirst prepare the non-water reversed-phase emulsion of diamine monomer, then dianhydride monomer is progressively added in this emulsion and react and form polyamidesAmino acid emulsion obtains medlin particulate after heat or chemical imidization. There is productive rate in medlin particulate prepared by the methodLow, particle size and particle diameter distribute and are difficult to the defects such as control.
Most of presoma-polyamic acid the particulate of first preparing medlin particulate that adopts of above-mentioned technique, then by it in heat or changeLearn under imidization effect and be converted into medlin particulate. The method exists that preparation process is loaded down with trivial details, process route is complicated, finally producesThe defects such as it is wide that thing purity is not high, productive rate is low, particle diameter distributes. The people such as Nagata (Polymer, 1996,11:980-985) are with respectivelyKind of dianhydride, diamines are reactant, and NMP is solvent, first synthesizing polyamides acid, then by polyamic acid homogeneous phase solution at 180 DEG CUnder condition, heat 4h, obtain the polyimide powder of high crystalline. The people such as Wakabayashi(Polymer, 2007,48:458-466) utilizes phase separation method to prepare medlin particulate, and they first prepare a series of polyamideAcid oligomer thing, prepares the medlin particulate of different morphologies by changing solvent, concentration and reaction temperature. Above-mentioned technique firstMake homogeneous phase polyamic acid solution, in imidization process, separate out medlin particulate, technique is simple, and product purity is high, butIn preparation process, influence factor is many, and process conditions are difficult to be controlled, poor repeatability.
Summary of the invention
For the problems referred to above, the object of the present invention is to provide a kind of preparation method of medlin particulate, its technique is simple,Productive rate is high, reproducible, thereby is suitable for industrial production.
The object of the present invention is achieved like this: a kind of preparation method of medlin particulate, is characterized in that comprising following stepRapid: (1), by dianhydride monomer and excessive fatty alcohol hybrid reaction under catalyst action, obtains ester-acid derivative; (2) willEster-the acid derivative that obtains mixes in polar non-proton organic solvent with diamine monomer, in 130-200 DEG C of stirring reaction6～48h, obtains medlin particulate through separating, wash, being dried.
Technique of the present invention is simple, and productive rate is high, reproducible, thereby is suitable for industrial production, and prepared polyimides is micro-Grain, has degree of crystallinity high, the features such as stable performance, specific area are high, compound with regular structure.
Brief description of the drawings
Fig. 1 is X-ray powder diffraction (XRD) figure of embodiment 1 polyimides of preparing gained.
Fig. 2 is ESEM (SEM) figure that embodiment 1 prepares the polyimides of gained.
Fig. 3 is X-ray powder diffraction (XRD) figure of embodiment 2 polyimides of preparing gained.
Fig. 4 is ESEM (SEM) figure that embodiment 2 prepares the polyimides of gained.
Fig. 5 is X-ray powder diffraction (XRD) figure of embodiment 3 polyimides of preparing gained.
Fig. 6 is ESEM (SEM) figure that embodiment 3 prepares the polyimides of gained.
Fig. 7 is X-ray powder diffraction (XRD) figure of embodiment 4 polyimides of preparing gained.
Fig. 8 is ESEM (SEM) figure that embodiment 4 prepares the polyimides of gained.
Fig. 9 is X-ray powder diffraction (XRD) figure of embodiment 5 polyimides of preparing gained.
Figure 10 is ESEM (SEM) figure that embodiment 5 prepares the polyimides of gained.
Figure 11 is X-ray powder diffraction (XRD) figure of embodiment 6 polyimides of preparing gained.
Figure 12 is ESEM (SEM) figure that embodiment 6 prepares the polyimides of gained.
Figure 13 is X-ray powder diffraction (XRD) figure of embodiment 7 polyimides of preparing gained.
Figure 14 is ESEM (SEM) figure that embodiment 7 prepares the polyimides of gained.
Figure 15 is X-ray powder diffraction (XRD) figure of embodiment 8 polyimides of preparing gained.
Figure 16 is ESEM (SEM) figure that embodiment 8 prepares the polyimides of gained.
Figure 17 is X-ray powder diffraction (XRD) figure of embodiment 9 polyimides of preparing gained.
Figure 18 is ESEM (SEM) figure that embodiment 9 prepares the polyimides of gained.
Detailed description of the invention
The present invention is a kind of preparation method of medlin particulate, comprises the following steps:
(1) by dianhydride monomer and excessive fatty alcohol hybrid reaction under catalyst action, obtain Zhi ?acid derivative;
(2) by obtained Zhi ?acid derivative mix in polar non-proton organic solvent with diamine monomer, in 130 ?200 DEG C of stirring reaction 6～48h, obtain medlin particulate through separating, wash, being dried. Wherein, diamine monomer can be fatFat diamines or aromatic diamines.
Preferably, described diamine monomer and dianhydride monomer gross mass account for the 0.5-50% of reaction mass gross mass, diamine monomer and twoThe mol ratio of anhydride monomer is 1:(0.99～1.1).
Preferably, in described step (1), the general structure of described dianhydride monomer is:
Wherein, Ar1For one or more in following structural formula group:
Wherein, R1～R24Be respectively hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group,Carbon number is 1～4 alkyl or pi-allyl; R25Be selected from one or more in following radicals:
—CO—、—O—、—S—、—SO2—、—CH2—、—C(CH3)2—、—C(CF3)2—、—O—R26—O—
Wherein R26Any in following structural formula group:
Wherein, R27～R121Be respectively hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group,Carbon number is 1～4 alkyl or pi-allyl.
Preferably, in described step (1), described fatty alcohol be selected from methyl alcohol, ethanol, isopropyl alcohol, normal propyl alcohol, the tert-butyl alcohol,N-butanol, isobutanol, sec-butyl alcohol, isoamyl alcohol, n-amyl alcohol, sec-amyl alcohol, tert-pentyl alcohol, n-hexyl alcohol, n-octyl alcohol, secondary octanol,One in isooctanol, Decanol, n-heptanol, undecyl alcohol, lauryl alcohol, tridecanol, tetradecyl alchohol, cyclohexanol, cyclopentanolOr two or more mixture.
Preferably, in described step (1), described catalyst is triethylamine or other tertiary amine compounds.
Preferably, in described step (2), described diamine monomer is selected from one in aromatic diamine monomers or aliphatic diamine monomerPlant or two kinds of mixing.
Described aromatic diamine monomers is selected from one or more in compound shown in following general structure:
NH2-Ar2-NH2
Wherein, Ar2Be respectively and be selected from any of following structural formula:
Wherein, R122～R280Be selected from hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group,Carbon number is 1～4 alkyl or pi-allyl; R281Be selected from the one in following radicals:
—CONH—、—CO—、—O—、—S—、—S—S—、—SO2—、—CH2—、—C(CH3)2—、—C(CF3)2—、—O—R304—O—
Wherein, R282～R303Be selected from hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group,Carbon number is 1～4 alkyl or pi-allyl; R304Be selected from the one in following radicals:
Wherein, R305～R376Be selected from hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group,Carbon number is 1～4 alkyl or pi-allyl.
Preferably, in described step (2), described aliphatic diamine monomer is selected from the one in compound shown in following general structureOr two or more:
NH2-(CH2)n-NH2
Wherein, n=2～12;
Preferably, in described step (2), described polar non-proton organic solvent is selected from 1-METHYLPYRROLIDONE, dimethylSulfoxide, dimethyl sulfone, sulfolane, Isosorbide-5-Nitrae-dioxane, DMA, DMF, isophthalicThe mixture of one or more in phenol, o-dichlorohenzene.
Below in conjunction with specific embodiment, the present invention is further set forth, it is important to point out that following examples can not be interpreted as rightThe restriction of invention protection domain, some non-of the present invention being made according to foregoing invention content of the person skilled in the art in this fieldThe improvement of matter and adjustment, must belong to protection scope of the present invention.
Embodiment 1
By 3,3`, 4,4-benzophenone tetracarboxylic dianhydride (BTDA), p-phenylenediamine (PPD) (PDA) and Putriscine (DBA) systemStandby copolyimide particulate.
By 3.2223g(10mmol) BTDA adds in 100ml there-necked flask, and adds 50ml ethanol and 1.5ml tri-secondAmine, is heated to 120 DEG C and carries out first step reaction, after reaction 1h, unnecessary ethanol distillation out, leaves tool stickingEster-acid derivative; Then add respectively 0.8651g(8mmol) PDA, 0.1763g (2mmol) DBA and 42.64g weightThe vapor of mixture solvent that amount forms than the 1-METHYLPYRROLIDONE (NMP) for 4:1 and o-dichlorohenzene (o-DCB), addsHeat, to 150 DEG C, stirs, and after reaction 24h, finishes reaction, and suction filtration, obtains medlin particulate, is placed in 200 DEG C of vacuum drying ovensDry 24h down. 5% thermal weight loss temperature of this copolyimide particulate is 503.9 DEG C, and BET specific area is 58m2g-1，The X-ray powder diffraction pattern of copolyimide particulate, scanning electron microscope (SEM) photograph are as shown in accompanying drawing 1-2.
Embodiment 2
By 3,3`, 4,4-benzophenone tetracarboxylic dianhydride (BTDA), 4,4 '-diaminodiphenyl ether (ODA) and Putriscine (DBA)Prepare copolyimide particulate.
By 3.2223g(10mmol) BTDA adds in 100ml there-necked flask, and adds 50ml ethanol and 1.5ml tri-secondAmine, is heated to 120 DEG C and carries out first step reaction, after reaction 1h, unnecessary ethanol distillation out, leaves tool stickingEster-acid derivative; Then add respectively 1.4017g(7mmol) ODA, 0.2645g (3mmol) DBA and 48.89g weightThe vapor of mixture solvent forming than the 1-METHYLPYRROLIDONE (NMP) for 4:1 and o-dichlorohenzene (o-DCB), heatingTo 150 DEG C, stir, after reaction 24h, finish reaction, suction filtration, obtains medlin particulate, is placed in 200 DEG C of vacuum drying ovensDry 24h down. 5% thermal weight loss temperature (N of this copolyimide particulate2Atmosphere) be 505.0 DEG C, BET specific surfaceAmass as 62m2g-1, the X-ray powder diffraction pattern of copolyimide particulate, scanning electron microscope (SEM) photograph are as shown in accompanying drawing 3-4.
Embodiment 3
By 3,3`, 4,4-benzophenone tetracarboxylic dianhydride (BTDA), 4,4 '-diaminobenzene anilid (DABA) and Isosorbide-5-Nitrae-Ding bis-Amine (DBA) is prepared copolyimide particulate.
By 3.2223g(10mmol) BTDA adds in 100ml there-necked flask, and adds 50ml ethanol and 1.5ml tri-secondAmine, is heated to 120 DEG C and carries out first step reaction, after reaction 1h, unnecessary ethanol distillation out, leaves tool stickingEster-acid derivative; Then add respectively 1.5908g(7mmol) DABA, 0.2645g (3mmol) DBA and 50.78g weightThe vapor of mixture solvent that amount forms than the 1-METHYLPYRROLIDONE (NMP) for 4:1 and o-dichlorohenzene (o-DCB), addsHeat, to 150 DEG C, stirs, and after reaction 24h, finishes reaction, and suction filtration, obtains medlin particulate, is placed in 200 DEG C of vacuum drying ovensDry 24h down. 5% thermal weight loss temperature of this copolyimide particulate is 495.2 DEG C, and BET specific area is 82m2g-1，The X-ray powder diffraction pattern of copolyimide particulate, scanning electron microscope (SEM) photograph are as shown in accompanying drawing 5-6.
Embodiment 4
By 4,4 '-Biphenyl Ether dianhydride (OPDA), p-phenylenediamine (PPD) (PDA) are prepared copolymerization polyamides with Putriscine (DBA)Imines particulate.
By 3.1022g(10mmol) OPDA adds in 100ml there-necked flask, and adds 50ml ethanol and 1.5ml tri-secondAmine, is heated to 120 DEG C and carries out first step reaction, after reaction 1h, unnecessary ethanol distillation out, leaves tool stickingEster-acid derivative; Then add respectively 0.9733g(9mmol) PDA, 0.0888g (1mmol) DBA and 41.64g weightThe vapor of mixture solvent forming than the 1-METHYLPYRROLIDONE (NMP) for 4:1 and o-dichlorohenzene (o-DCB), heatingTo 150 DEG C, stir, after reaction 24h, finish reaction, suction filtration, obtains medlin particulate, is placed in 200 DEG C of vacuum drying ovensDry 24h down. 5% thermal weight loss temperature of this copolyimide particulate is 536.3 DEG C, and BET specific area is 32m2g-1，The X-ray powder diffraction pattern of copolyimide particulate, scanning electron microscope (SEM) photograph are as shown in accompanying drawing 7-8.
Embodiment 5
By 4,4 '-Biphenyl Ether dianhydride (OPDA), 4,4 '-benzidine (BZD) is prepared copolymerization with Putriscine (DBA)Medlin particulate.
By 3.1022g(10mmol) OPDA adds in 100ml there-necked flask, and adds 50ml ethanol and 1.5ml tri-secondAmine, is heated to 120 DEG C and carries out first step reaction, after reaction 1h, unnecessary ethanol distillation out, leaves tool stickingEster-acid derivative; Then add respectively 1.2897g(7mmol) BZD, 0.2645g (3mmol) DBA and 46.56g weightThe vapor of mixture solvent that amount forms than the 1-METHYLPYRROLIDONE (NMP) for 4:1 and o-dichlorohenzene (o-DCB), addsHeat, to 150 DEG C, stirs, and after reaction 24h, finishes reaction, and suction filtration, obtains medlin particulate, is placed in 200 DEG C of vacuum drying ovensDry 24h down. 5% thermal weight loss temperature of this copolyimide particulate is 518.4 DEG C, and BET specific area is 41m2g-1，The X-ray powder diffraction pattern of copolyimide particulate, scanning electron microscope (SEM) photograph are as shown in accompanying drawing 9-10.
Embodiment 6
By 4,4 '-Biphenyl Ether dianhydride (OPDA), 4,4 '-diaminobenzene anilid (DABA) and Putriscine (DBA)Prepare copolyimide particulate.
By 3.1022g(10mmol) OPDA adds in 100ml there-necked flask, and adds 50ml ethanol and 1.5ml tri-secondAmine, is heated to 120 DEG C and carries out first step reaction, after reaction 1h, unnecessary ethanol distillation out, leaves tool stickingEster-acid derivative; Then add respectively 1.5908g(7mmol) DABA, 0.2645g (3mmol) DBA and 49.58g weightThe vapor of mixture solvent that amount forms than the 1-METHYLPYRROLIDONE (NMP) for 4:1 and o-dichlorohenzene (o-DCB), addsHeat, to 150 DEG C, stirs, and after reaction 24h, finishes reaction, and suction filtration, obtains medlin particulate, is placed in 200 DEG C of vacuum drying ovensDry 24h down. 5% thermal weight loss temperature of this copolyimide particulate is 504.3 DEG C, and BET specific area is 17m2g-1，The X-ray powder diffraction pattern of copolyimide particulate, scanning electron microscope (SEM) photograph are as shown in accompanying drawing 11-12.
Embodiment 7
Prepare copolymerization polyamides by pyromellitic acid anhydride (PMDA), p-phenylenediamine (PPD) (PDA) with Putriscine (DBA)Imines particulate.
By 2.1812g(10mmol) PMDA adds in 100ml there-necked flask, and adds 50ml ethanol and 1.5ml tri-secondAmine, is heated to 120 DEG C and carries out first step reaction, after reaction 1h, unnecessary ethanol distillation out, leaves tool stickingEster-acid derivative; Then add respectively 0.7570g(7mmol) PDA, 0.2645g (3mmol) DBA and 32.03g weightThe vapor of mixture solvent forming than the 1-METHYLPYRROLIDONE (NMP) for 4:1 and o-dichlorohenzene (o-DCB), heatingTo 150 DEG C, stir, after reaction 24h, finish reaction, suction filtration, obtains medlin particulate, is placed in 200 DEG C of vacuum drying ovensDry 24h down. 5% thermal weight loss temperature of this copolyimide particulate is 510.1 DEG C, and BET specific area is 122m2g-1，The X-ray powder diffraction pattern of copolyimide particulate, scanning electron microscope (SEM) photograph are as shown in accompanying drawing 13-14.
Embodiment 8
By pyromellitic acid anhydride (PMDA), 4,4 '-diaminodiphenyl ether (ODA) and Putriscine (DBA) preparationCopolyimide particulate.
By 2.1812g(10mmol) PMDA adds in 100ml there-necked flask, and adds 50ml ethanol and 1.5ml tri-secondAmine, is heated to 120 DEG C and carries out first step reaction, after reaction 1h, unnecessary ethanol distillation out, leaves tool stickingEster-acid derivative; Then add respectively 1.4017g(7mmol) ODA, 0.2645g (3mmol) DBA and 38.47g weightThe vapor of mixture solvent forming than the 1-METHYLPYRROLIDONE (NMP) for 4:1 and o-dichlorohenzene (o-DCB), heatingTo 150 DEG C, stir, after reaction 24h, finish reaction, suction filtration, obtains medlin particulate, is placed in 200 DEG C of vacuum drying ovensDry 24h down. 5% thermal weight loss temperature of this copolyimide particulate is 487.5 DEG C, and BET specific area is 90m2g-1，The X-ray powder diffraction pattern of copolyimide particulate, scanning electron microscope (SEM) photograph are as shown in accompanying drawing 15-16.
Embodiment 9
By pyromellitic acid anhydride (PMDA), 4,4 '-diaminodiphenyl sulfide (SDA) and Putriscine (DBA) systemStandby copolyimide particulate.
By 2.1812g(10mmol) PMDA adds in 100ml there-necked flask, and adds 50ml ethanol and 1.5ml tri-secondAmine, is heated to 120 DEG C and carries out first step reaction, after reaction 1h, unnecessary ethanol distillation out, leaves tool stickingEster-acid derivative; Then add respectively 1.5141g(7mmol) SDA, 0.2645g (3mmol) DBA and 39.60g weightThe vapor of mixture solvent forming than the 1-METHYLPYRROLIDONE (NMP) for 4:1 and o-dichlorohenzene (o-DCB), heatingTo 150 DEG C, stir, after reaction 24h, finish reaction, suction filtration, obtains medlin particulate, is placed in 200 DEG C of vacuum drying ovensDry 24h down. 5% thermal weight loss temperature of this copolyimide particulate is 507.6 DEG C, and BET specific area is 116m2g-1，The X-ray powder diffraction pattern of copolyimide particulate, scanning electron microscope (SEM) photograph are as shown in accompanying drawing 17-18.
Embodiment 10
Prepare medlin particulate by pyromellitic acid anhydride (PMDA), p-phenylenediamine (PPD) (PDA).
By 2.1812g(10mmol) PMDA adds in 100ml there-necked flask, and adds 50ml ethanol and 1.5ml tri-secondAmine, is heated to 120 DEG C and carries out first step reaction, after reaction 1h, unnecessary ethanol distillation out, leaves tool stickingEster-acid derivative; Then add respectively 1.0814g(10mmol) PDA and the 32.03g weight ratio N-methyl pyrrole that is 4:1Pyrrolidone (NMP) and the vapor of mixture solvent that o-dichlorohenzene (o-DCB) forms, be heated to 150 DEG C, stirs, anti-Answer after 24h and finish reaction, suction filtration, obtains medlin particulate, is placed in dry 24h at 200 DEG C of vacuum drying ovens.
Embodiment 11
Prepare medlin particulate by pyromellitic acid anhydride (PMDA), Putriscine (DBA).
By 2.1812g(10mmol) PMDA adds in 100ml there-necked flask, and adds 50ml ethanol and 1.5ml tri-secondAmine, is heated to 120 DEG C and carries out first step reaction, after reaction 1h, unnecessary ethanol distillation out, leaves tool stickingEster-acid derivative; Then add respectively the N-methylpyrrole that 0.8817g (10mmol) DBA and 32.03g weight ratio are 4:1Alkane ketone (NMP) and the vapor of mixture solvent that o-dichlorohenzene (o-DCB) forms, be heated to 150 DEG C, stirs reactionAfter 24h, finish reaction, suction filtration, obtains medlin particulate, is placed in dry 24h at 200 DEG C of vacuum drying ovens.
Claims (7)
1. a preparation method for medlin particulate, is characterized in that comprising the following steps:
(1) by dianhydride monomer and excessive fatty alcohol hybrid reaction under catalyst action, obtain Zhi ?acid derivativeThing, the general structure of dianhydride monomer is wherein:
Wherein, Ar1For one or more in following structural formula group:
Wherein, R1～R24Be respectively hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyAlkyl or pi-allyl that base, ester group, carbon number are 1～4; R25Be selected from one or both in following radicalsAbove:
—CO—、—O—、—S—、—SO2—、—CH2—、—C(CH3)2—、—C(CF3)2—、—O—R26—O—
Wherein R26Any in following structural formula group:
Wherein, R27～R121Be respectively hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyAlkyl or pi-allyl that base, ester group, carbon number are 1～4;
(2) by obtained Zhi ?acid derivative mix in polar non-proton organic solvent with diamine monomer,In 130 ?200 DEG C of stirring reaction 6～48h, through separating, washing, dry obtain medlin particulate, whereinDescribed diamine monomer is one or both in aliphatic diamine or aromatic diamines.
2. the preparation method of medlin particulate according to claim 1, is characterized in that: described twoAmine monomers and dianhydride monomer gross mass account for the 0.5-50% of reaction mass gross mass, diamine monomer and dianhydride monomerMol ratio is 1:(0.99～1.2).
3. the preparation method of medlin particulate according to claim 1, is characterized in that: described stepSuddenly in (1), described fatty alcohol be selected from methyl alcohol, ethanol, isopropyl alcohol, normal propyl alcohol, the tert-butyl alcohol, n-butanol,Isobutanol, sec-butyl alcohol, isoamyl alcohol, n-amyl alcohol, sec-amyl alcohol, tert-pentyl alcohol, n-hexyl alcohol, n-octyl alcohol, secondary octanol,Isooctanol, Decanol, n-heptanol, undecyl alcohol, lauryl alcohol, tridecanol, tetradecyl alchohol, cyclohexanol, cyclopentanolIn one or more mixture.
4. the preparation method of medlin particulate according to claim 1, is characterized in that: described stepSuddenly in (1), described catalyst is triethylamine.
5. the preparation method of medlin particulate according to claim 1, is characterized in that: describedAromatic diamines, general structure is as follows:
NH2-Ar2-NH2
Wherein, Ar2Be respectively and be selected from any of following structural formula:
Wherein, R122～R280Be selected from hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyAlkyl or pi-allyl that base, ester group, carbon number are 1～4; R281Be selected from the one in following radicals:
—CONH—、—CO—、—O—、—S—、—S—S—、—SO2—、—CH2—、—C(CH3)2—、—C(CF3)2—、—O—R304—O—
Wherein, R282～R303Be selected from hydrogen, halogen family substituting group, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyAlkyl or pi-allyl that base, ester group, carbon number are 1～4; R304Be selected from the one in following radicals:
Wherein, R305～R376Be selected from hydrogen, phenyl ring, carboxylate radical, hydroxyl, cyano group, methoxyl group, ester group, carbonAtomicity is 1～4 alkyl or pi-allyl.
6. the preparation method of medlin particulate according to claim 1, is characterized in that: described stepSuddenly in (2), described aliphatic diamine, general structure is:
NH2-(CH2)n-NH2
Wherein, n=2～12.
7. the preparation method of medlin particulate according to claim 1, is characterized in that: described stepSuddenly in (2), described polar non-proton organic solvent is selected from 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), diformazanBase sulfone, sulfolane, Isosorbide-5-Nitrae-dioxane, DMA, DMF, a phenol,The mixture of one or more in o-dichlorohenzene.
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| CN101190968A (en) * | 2006-11-27 | 2008-06-04 | 中国科学院化学研究所 | Polyimide resin and preparation method thereof |
| CN101230136A (en) * | 2007-01-22 | 2008-07-30 | 东丽纤维研究所（中国）有限公司 | Polyimide microparticle and preparation method thereof |
| CN102604092A (en) * | 2012-02-20 | 2012-07-25 | 中国科学院化学研究所 | Polyimide resin as well as preparation method and application thereof |
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| US20110316177A1 (en) * | 2009-12-22 | 2011-12-29 | E.I. Du Pont De Nemours And Company | Polyimide particles derived from scrap polyimide film and methods relating thereto |
| FR2980204B1 (en) * | 2011-09-20 | 2015-03-27 | Rhodia Operations | NOVEL (CO) THERMOPLASTIC POLYIMIDES AND METHODS OF SYNTHESIS |
| CN102850569B (en) * | 2012-09-20 | 2014-05-21 | 中国科学院长春应用化学研究所 | Preparation method of polyimide foam |
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| CN101190968A (en) * | 2006-11-27 | 2008-06-04 | 中国科学院化学研究所 | Polyimide resin and preparation method thereof |
| CN101230136A (en) * | 2007-01-22 | 2008-07-30 | 东丽纤维研究所（中国）有限公司 | Polyimide microparticle and preparation method thereof |
| CN102604092A (en) * | 2012-02-20 | 2012-07-25 | 中国科学院化学研究所 | Polyimide resin as well as preparation method and application thereof |
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